Urethane derivatives of polymethyl biphenyl useful as fungicides

ABSTRACT

Novel urethane derivatives of polymethyl biphenyl useful as fungicides and also having insecticidal, miticidal and nematocidal activities are disclosed. These products are prepared by reacting the appropriate alkyl or aryl isocyanate with the hydroxy polymethylbiphenyl at temperatures of 0* to 35*C. to produce the corresponding urethane derivatives of polymethyl biphenyl.

United States Patent [1 1 Fields et al.

[451 Apr. 29, 1975 URETIIANE DERIVATIVES OF POLYMETIIYL BIPHENYL USEFUL AS FUNGICIDES [75] Inventors: Ellis K. Fields, River Forest; Imre Puskas, Glen Ellyn, both of I11.

[73] Assignee: Standard Oil Company, Chicago, Ill.

[22] Filed: Jan. 24, 1972 [21] App]. No.: 220,367

[52] U.S. Cl 260/471 C; 71/111; 260/479 C;

424/300 [51] Int. Cl. C07c 125/06 [58] Field of Search 260/471 C, 479 C [56] References Cited UNITED STATES PATENTS 3,632,631 l/l972 Wright 260/479 C Primary ExaminerLorraine A. Weinberger Assistant Examiner-L. A. Thaxton Attorney, Agent, or FirmGunar J. Blumberg; Arthur G. Gilkes; William T. McClain [57] ABSTRACT 17 Claims, No Drawings 1 URETIIANE DERIVATIVES OF POLYMETHYL BIPHENYL USEFUL AS FUNGICIDES This invention relates to novel urethane derivatives of polymethyl biphenyl. More particularly, this invention relates to urethane derivatives of polymethyl biphenyls having the following formula:

wherein the amino group occupies the 2 or 3 position on the phenyl ring and R and R are methyl groups and n and m are integers having values from 2 to 4 inclusive are diazotized and hydrolyzed as described in J. Organic Chemistry 33, 4237 (1968) to produce the phenols having the following structure:

These phenols are reacted with the appropriate alkyl or aryl isocyanate under anhydrous conditions withpyridine or dibutyltindiacetate catalysts to obtain the urethane compounds shown on page 1.

A best mode for preparing one of the novel biphenyl urethanes follows:

To a stirred solution of 3-hydroxy-2,3', 4,4, 6-pentamethylbiphenyl in methylene dichloride, methyl isocyanate and dibutyltindiacetate were added. Approximately one hour later the solvents were removed in vacuo and a foamy solid of the product 2,3,4,4',6- pentamethylbiphenyl-3-yl-N-methyl carbamate melting around 5765C. was recovered. It was characterized by infrared spectroscopy showing characteristic bands at 3250 and 1710 cm- The product, upon testing for foliar fungicidal efficacy, showed effective control for bean mildew, bean rust and leaf rust of wheat and other uses as shown in Tables I and II.

The following novel urethane biphenyls were prepared:

2,3', 4,4, 6-pentamethylbiphenyl-3-yl-N-methyl carbamate 3', 4,4',S-tetramethylbiphenyl-2-yl-N-ethyl carbamate 3',4,4, 5-tetramethylbiphenyl-2-yl-N-n-propyl carbamate 3',4,4,5-tetramethylbiphenyl-2-yl-N-methyl carbamate 2,3,4,4',6-pentamethylbiphenyl-3-yl-N-ethyl bamate 2,3, carbamate 2,3 ',4,4 ',6-pentamethylbiphenyl-3-yl-N-phenyl carbamate 2,3 ',4,4 ,6-pentamethylbiphenyl-3-yl-N-onitrophenyl carbamate 2,3 ',4,4 ',6-pentamethylbiphenyl-3-yl-N-ochlorophenyl carbamate 3 ',4,4',5-tetramethylbiphenyl-2-yl-N-phenyl carbamate 3',4,4,5-tetramethylbiphenyI-2-yl-N-o-nitrophenyl carbamate car- 4,4',6-pentamethylbiphenyl-3-yl-N-n-propyl 3',4,4,5-tetramethylbiphenyl-2-yl-N-o-chlorophenyl carbamate 3 ',4,4 ,5-tetramethylbiphenyl-2-yl-N-m-nitrophenyl carbamate 2,3 ',4,4 ,6-pentamethylbiphenyl- 3-yl-N-mnitrophenyl carbamate 2 ',4,4 ,5 ,5 -pentamethylbiphenyl-2-yl-N-methyl carbamate 3,3,4,4',5,6-hexamethylbiphenyl-Z-yl-N-methyl carbamate The invention is further illustrated in the following examples:

EXAMPLE I and 1720 cm, respectively (in Nujol mull).

3 4 TABLE I EXAMPLE V Ethyl isocyanate (0.9 g.) and dibutyltindiacetate :2 :50 2352 3 253:? "53? (two drops) were added to a stirred solution of 3- (p. .m.) 5 hydroxy-2,3',4,4,6-pentamethylbiphenyl (2.0 g.) in Bean Mildew Product of Example I 100 100 methylene dichloride ml.). The reaction flask with 50 100 an open neck was placed into a hood. A syrup was left Bean Rust Product of Examplcl 5g after slow evaporation of the solvents that became a 50 100 foamy solid on vacuum drying at 0.1 mm. This crude Leaf Rust 99 10 2,3',4,4,6-pentamethylbiphenyl-3-yl-N-ethyl carbamof wheat Product of Example! 100 97 ate melted in the -50C. range. Its IR spectrum 50 75 showed the Nl-I and C=O bands at 3300 and 1725 25 39 (broad) cm, respectively (in Nujol mull).

TABLE II FOLIAR FUNGICIDAL EFFICACY OF 2,3',4,4',6-PEN'IAMETHYL-3-yLN-METHYL CARBAMATE Disease Control of Conc. Earl Late Leaf Powdery Leaf Rice Bean Bean Wheat PPM Blig t Blight Rust Mildew Spot Blast Rust Mildew Mildew EXAMPLE ll EXAMPLE VI Ethy is y g-) and dibutyltindiacetate 3O n-Propyl isocyanate (0.9 g.) and dibutyltindiacetate (one drop) were added to a stirred Solution of 2- (2 drops) were added to a stirred solution of 3- hy y- 3 y p y g-) in hydroxy-2,3,4,4,-pentamethylbiphenyl (2.13 g.) in m thyl n dichloride The reaction flask with methylene dichloride (15 ml.). The reaction flask with an open neck was placed into a hOOd. On SlOW evaporaan open neck was placed into a hood, A syrup was left tion of the solvents Crystals depOSi ed- These Were 35 after slow evaporation of the solvents. This was vacuum washed with heXane-Cai' n tetrachloride The dried at 0.1 mm. Residue was dissolved in hexane. On White Product, y p y I slow evaporation of the solvent the product, 2,3',4,4',- ethyl Carbamate melted unsharp around 6-pentamethylbiphenyl-3-yl-N-n-propyl carbamate, 700-9000 Its IR Spectrum Showed the and C=O separated in a crystalline form, m.p. 869lC. Its IR bands at 3250 and 1710 m, re p iv y Nujol spectrum showed the NH and C=O bands at 3270 mull). and 1710 cm", respectively (in Nujol mull).

EXAMPLE EXAMPLE v11 n-Propyl isocyanate (0.9 g.) and dibutyltindiacetate (1 drop) were added to a stirred solution of 2-hydroxyg l g ggg iggz q 'g g i g i g gsg g i zg gfi i 3f44""etramethylbiphenyl methylene hydroxy-2,3',4,4',6-pentamethylbiphenyl (1.6 g.) in dlchlonde (15 l The reacnon flask wlth an open methylene dichloride. After overnight standing the solneck was.placed mto hood A .Syrup wasdeft after Slow vent was removed in vacuo. The residue crystallized on evaporation of the solvents. This crystallized slowly on Scratchin in the resence of a few dm 5 of hexane being triturated with hexane. The white product, 3',4,- The g p g 2 4 6 pemamepthylbiphenyll 4',5-tetramethylbi hen yl-Z yI-N-n-propyl carbamate, 3 yl N phenyl carbama;e z y other name, (2'25 melted at 54 60 23 5 2? ff 6-pentamethylbiphenyl-3-yl carbanilate), melted at the cfobands at 33 cm 154-155c. Its IR spectrum showed the N-H and Spectwely (m Nujol C=O bands at 3250 and 1720 cm, respectively (in EXAMPLE IV Nujol mull).

Methyl isocyanate (2.2 ml., in excess) and dibutyltindiacetate (1 drop) were added to a stirred solution EXAMPLE of 2-hydroxy-3,4,4',5-tetramethylbiphenyl (2.25 g.) in o-Nitrophenylisocyanate (1.15 g, Eastman Organic methylene dichloride (15 ml.). One hour later the s01- Chemicals) was dissolved in methylene dichloride and vents were removed in vacuo. Residual syrup slowly filtered from the insolubles. The filtrate and triethylamcrystallized on being triturated with hexane. The white ine (three drops) were added to a stirred solution of 3- product, 3,4,4',5-tetramethylbiphenyl-2-yl-N-methyl hydroxy-2,3',4,4',o-pentamethylbiphenyl (1.5 g.) in carbamate (2.78 g.) melted at 76.578.5C. Its IR methylene dichloride (10ml). The workup procedure spectrum showed the N-l-l and C=O bands at 3300 of Example VII gave a pale yellow crystalline powder,

2,3 ',4,4',6-pentamethylbiphenyl-3-yl-N-o-nitrophenyl carbamate (or, by other name, 2,3,4,4',6-pentamethylbiphenyl-3-yl o-nitro-carbanilate), (2.26 g) m.p. l-127C. Its IR spectrum showed the NH and C=O bands at 3280 and 1755 cm, respectively (in Nujol mull).

EXAMPLE IX The reaction and workup was similar to Example VIII but, in place of o-nitrophenylisocyanate, ochlorophenylisocyanate was used. The white product, 2,3 ,4,4 ,6-pentamethylbiphenyl-3-yl-N-ochlorophenyl carbamate (or, by other name, 2,3',4,4',- 6-pentamethylbiphenyl-3-yl o-chlorocarbanilate) (crude) melted at 93-97C.

EXAMPLE X Phenyl isocyanate (0.8 g.) and 2-hydroxy-3',4,4',5- tetramethylbiphenyl (1.5 g.) were dissolved in methylene dichloride ml.). Two drops of anhydrous triethylamine were added. After overnight standing the solvent was removed in vacuo and the residue crystallized in contact with hexane. The white product, 3,4,4,5- tetramethylbiphenyl-2-yl-N-phenyl carbamate (or, by other name, 3,4,4',5-tetramethylbiphenyl-2-yl carbanilate) (2.17 g.) melted at 130l32C. Its IR spectrum showed the NH and C=O bands at 3240 and 1716 and 1732 (split) cm, respectively (in Nujol mull).

EXAMPLE XI The reaction and workup was similar to Example X, but in place of phd nylisocyanate, o-

nitrophenylisocyanate 1.15 g.) was used. The pale yellow product, 3',4,4',5-tetramethylbiphenyl-Z-yl-N-onitrophenyl carbamate (or, by alternative name, 3',4,4- ',5 -tetramethylbiphenyl-2-yl o-nitrocarbanilate melted at l31133C. Its IR spectrum showed the expected N--H and C=O bands at 3340 and 1770 cm, respectively (in Nujol mull).

EXAMPLE XII The reaction and the workup was similar to Example X, but in place of phenylisocyanate, ochlorophenylisocyanate was used. The crude white product, 3 ',4,4 ',5 -tetramethylbiphenyl-2-yl-N-ochlorophenyl carbamate (or, by alternative name, 3,4- ,4 ,5 -tetramethylbiphenyl-2-yl 'o-chlorocarbanilate) melted at 8 l-85C. Its IR spectrum showed the NI-I and C=O bands at 3350 and 1755 cm", respectively (in Nujol mull).

EXAMPLE XIII solved in methylene dichloride (30 ml.). Two drops of anhydrous triethylamine were added. The workup method of Example X gave off-white product, 2,3 ',4,4- ',6-pentamethylbiphenyl-3-yl-N-m-nitrophenyl carbamate (2.49 g.) m.p. l62l65C. Its IR spectrum showed the N-I-I and C=O bands at 3240 and 1720 cm, respectively (in Nujol mull).

EXAMPLE XV Methyl isocyanate (2.0 ml.) and dibutyltindiacetate (4 drops) were added to a stirred solution of 2- hydroxy-2,4,4,5,5-pentamethylbiphenyl (1.9 g.) in methylene dichloride (15 ml.). After 30 minutes standing the mixture was refluxed for 20 minutes, and then taken to dryness in vacuo. Residual syrup crystallized in contact with hexane. The white product, 2,4,4',5,5 pentarnethylbiphenyl-2-yl-Nmethyl carbamate (2.3 g.) melted at 1 141 16C. Its IR spectrum showed the expected NH and C=O bands at 3320 and 1715 cm, respectively (in Nujol mull).

EXAMPLE XVI Methyl isocyanate (2.0 ml.) and dibutyltindiacetate (2 drops) were added to a stirred solution of 2- hydroxy-3,3',4,4',5,6-hexamethylbiphenyl (1.60 g.) in methylene dichloride 15 ml.). Two hours later the solvents were removed in vacuo. The residual syrup crystallized on being triturated with hexane. The white product, 3 ,3 ,4,4 ',5 ,6-hexamethylbiphenyl-2-yl-N- methyl carbamate (1.8 g.) melted 133C. Its IR spectrum showed the NH and C=O bands at 3320 and 1720 cm, respectively.

We claim:

1. A urethane derivative of polymethyl biphenyl having the following formula:

wherein the group occupies the 2 or 3 position on the phenyl ring, and wherein R is a lower alkyl, phenyl, nitrophenyl or chlorophenyl group, R and R are methyl groups and n and m are integers having values from 2 through 4, inclusive.

2. A urethane derivative of polymethyl biphenyl having the following formula:

I CO-NH- CH3 3. A urethane derivative of polymethyl biphenyl having the following formula:

J 3 f t CH 4. The compound of claim 1 wherein R is an ethyl group, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4',5 positions on the biphenyl rings and the group occupies the 2 position on the biphenyl ring.

5. The compound of claim 1 wherein R is a propyl group, n and m are integers each having a value of 2 and wherein the propyl groups are attached on the 4,5 and 4,5' positions on the biphenyl rings and the group occupies the 2 position on the biphenyl ring.

6. The compound of claim 1 wherein R is an ethyl group, n is an integer having a value of 3, and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4,5 positions on the biphenyl rings and the group occupies the 3 position on the biphenyl ring.

7. The compound of claim 1 wherein R is a propyl group, n is an integer having a value of 3, and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4,5' positions on the biphenyl rings and the group occupies the 3 position on the biphenyl ring.

8. The compound of claim 1 wherein R is a phenyl group, n is an integer having a value of 3, and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4,5 positions on the biphenyl rings and the groupoccupies the 3 position on the biphenyl ring.

9. The compound of claim 1 wherein R is a nitrophenyl group wherein the nitro group is attached in the ortho position on the phenyl ring, n is an integer having a value of 3, and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4,5 positions on the biphenyl rings and the group occupies the 3 position on the biphenyl ring.

10. The compound of claim 1 wherein R is a chlorophenyl group wherein the chlorine is attached in the ortho position on the phenyl ring, n is an integer having a value of 3 and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4',5 positions on the biphenyl rings and the group occupies the 3 position on the biphenyl ring.

11. The compound of claim 1 wherein R is a phenyl group, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4',5 positions on the biphenyl rings and the group occupies the 2 position on the biphenyl ring.

13. The compound of claim 1 wherein R is a chlorophenyl group wherein the chlorine is attached in the ortho position on the phenyl ring, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4,5 positions on the biphenyl rings and the group occupies the 2 position on the biphenyl ring.

14. The compound of claim 1 wherein R is a nitrophenyl group wherein the nitro group is attached in the meta position on the phenyl ring, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4,5 positions on the biphenyl rings and the group occupies the 3 position on the biphenyl ring.

16. The compound of claim 1 wherein R is a methyl group, n is an integer having a value of 2 and m is an integer having a value of 3 and wherein the methyl groups are attached on the 4,5 and 3,4,6' positions on the biphenyl rings and the group occupies the 2 position on the biphenyl ring.

17. The compound of claim 1 wherein R is a methyl group, n is an integer having a value of 4 and m is an integer having a value of 2, and wherein the methyl groups are attached on the 3,4,5,6 and 4,5 positions on the biphenyl ring, and the group occupies the 2 position on the biphenyl ring. 

1. A URETHANE DERIVATIVE OF POLYMETHYL BIPHENYL HAVING THE FOLLOWING FORMULA:
 2. A urethane derivative of polymethyl biphenyl having the following formula:
 3. A urethane derivative of polymethyl biphenyl having the following formula:
 4. The compound of claim 1 wherein R'' is an ethyl group, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4'',5'' positions on the biphenyl rings and the
 5. The compound of claim 1 wherein R'' is a propyl group, n and m are integers each having a value of 2 and wherein the propyl groups are attached on the 4,5 and 4'',5'' positions on the biphenyl rings and the
 6. The compound of claim 1 wherein R'' is an ethyl group, n is an integer having a value of 3, and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4'',5'' positions on the biphenyl rings and the
 7. The compound of claim 1 wherein R'' is a propyl group, n is an integer having a value of 3, and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4'',5'' positions on the biphenyl rings and the
 8. The compound of claim 1 wherein R'' is a phenyl group, n is an integer having a value of 3, and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4'',5'' positions on the biphenyl rings and the
 9. The compound of claim 1 wherein R'' is a nitrophenyl group wherein the nitro group is attached in the ortho position on the phenyl ring, n is an integer having a value of 3, and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4'',5'' positions on the biphenyl rings and the
 10. The compound of claim 1 wherein R'' is a chlorophenyl group wherein the chlorine is attached in the ortho position on the phenyl ring, n is an integer having a value of 3 and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4'',5'' positions on the biphenyl rings and the
 11. The compound of claim 1 wherein R'' is a phenyl group, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4'',5'' positions on the biphenyl rings and the
 12. The compound of claim 1 wherein R'' is a nitrophenyl group wherein the nitro group is attached in the ortho position on the phenyl ring, N and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4'',5'' positions on the biphenyl rings and the
 13. The compound of claim 1 wherein R'' is a chlorophenyl group wherein the chlorine is attached in the ortho position on the phenyl ring, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4'',5'' positions on the biphenyl rings and the
 14. The compound of claim 1 wherein R'' is a nitrophenyl group wherein the nitro group is attached in the meta position on the phenyl ring, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4'',5'' positions on the biphenyl rings and the
 15. The compound of claim 1 wherein R'' is a nitrophenyl group wherein the nitro group is attached in the meta position on the phenyl ring, n is an integer having a value of 3 and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4'',5'' positions on the biphenyl rings and the
 16. The compound of claim 1 wherein R'' is a methyl group, n is an integer having a value of 2 and m is an integer having a value of 3 and wherein the methyl groups are attached on the 4,5 and 3'',4'',6'' positions on the biphenyl rings and the
 17. The compound of claim 1 wherein R'' is a methyl group, n is an integer having a value of 4 and m is an integer having a value of 2, and wherein the methyl groups are attached on the 3,4,5,6 and 4'',5'' positions on the biphenyl ring, and the 